US2955932A - Hydrometallurgical process - Google Patents

Hydrometallurgical process Download PDF

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US2955932A
US2955932A US654080A US65408057A US2955932A US 2955932 A US2955932 A US 2955932A US 654080 A US654080 A US 654080A US 65408057 A US65408057 A US 65408057A US 2955932 A US2955932 A US 2955932A
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KERR MC GEE OIL IND Inc
KERR-MCGEE OIL INDUSTRIES Inc
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/28Amines
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/36Heterocyclic compounds
    • C22B3/362Heterocyclic compounds of a single type
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the water immiscible organic selective solvents may be acidic in nature such as the monoordi-alkyl hydrogen phosphates, or neutral in nature, such as the tri-alkyl phosphates, or basic in nature, such as the more recently developed organic amine selective solvent extractants.
  • the present invention is concerned only with those water immiscible organic selective solventswhich are either neutral or basic in nature and not with those which are acidic in nature.
  • the organic selective solvents which are acidic in nature are not suitable for use in accordance with the present invention.
  • waterinimiscible organic selective solvents which may be classified as neutral in nature, such as tri-butyl phosphate or other tri-alkyl phosphates, diethyl ether, hexane; and cetrain esters and ketones.
  • amines have activity in organic solvent extraction processes and are well known to the art.
  • the more satisfactory amine selec- 45 tive solvents are relatively high molecular weight and primary, secondary or tertiary alkyl amines (mono, di or tri-alkyl amines) which are insoluble in dilute acidic solutions.
  • the lower alkylated amines are, in general, soluble in dilute acid solutions and are not useful in solvent extraction processes, as is well understood in the art. Generally, as the size of the alkyl substituent increases, the corresponding amine salts become less and less soluble in water or dilute acid solutions and more soluble in organic solvents. Examples of suitable amines which have been found to be useful to various extents as organic selective solvent and which are very satisfactory in practicing the present invention are illustrated below in Table I. The amines illustrated therein are chosen at random and are intended as being only representative of a very large group of active amines.
  • the amine solvent normally being dissolved in a water immiscible inert organic solvent such as kerosene, naphtha, benzene, chloroform, etc.
  • a water immiscible inert organic solvent such as kerosene, naphtha, benzene, chloroform, etc.
  • the solution of amine in organic solvent is intimately contacted with an aqueous leach liquor containing metal values to be concentrated, thereby forming the amine-metal anion complex.
  • Successive contacts with fresh amine in organic solvent serves to transfer essentially the entire content of metal values to be concentrated from the aqueous leach liquor into the organic phase to thereby provide a metal loaded extraction solution.
  • This extraction solution then may be stripped with any suitable stripping agent to provide a concentrate of the extracted metal values in the stripping solution and a regenerated amine in water immiscible inert organic solvent.
  • the resulting strip solution is then further processed in accordance with prior art processes to produce a concentrate of the metal values or a metal containing product which, in turn, may be further processed to the desired metal.
  • the regenerated amine in water immiscible inert organic solvent may then be recycled in the process.
  • Turbidity in slightly dirty leach liquors is rarely attributable to the so-called sand fraction of the pulp, and is generally due to fractions of the finer, clayey slime portion.
  • the slime portion contains microscopic particles which resist settling in a thickener, or which may pass through a clarifying filter. Such particles are highly hydrated suspended clay fractions oflarge surface area and exhibit the usual ion exchange characteristics of clays. It is this property whichmost likely gives rise to the vicious emulsification tendencies of the above mentioned turbid liquors when contacted with the aminein-organic solvent and to lesser extent with other types of selective solvents.
  • the reagent must be strongly adsorbed by the solids or slimes in the leach liquor, largely saturating the ion exchange sites, and should not be desorbed and replaced by the selective solventduring the subsequent solventextraction step.
  • the reagent must be hydrophilic in nature and, after adsorption on the surfaces of the solids or slimes, form a hydrophilic exterior surface oriented toward the liquid-liquid system, thereby repelling the organic phase and being strongly wet by the aqueous phase.
  • the reagent should not. possess sufiicient surface-active properties to promote emulsification.
  • the reagent should be soluble in the presence of various anions and cations in the aqueous leach liquor, although certain reagents of somewhat limited solubility are effective due to the relatively small dosage required.
  • thereagent should be effective at low dosages and, from an economic standpoint, the reagent should be low in price.
  • a suitable extractant for the metal to beconcentrated such as a solution of tri-butyl phosphate or a suitable amine in kerosene.
  • polymeric amines and polymeric quaternary ammonium compounds which have been found to be very efiective are water or acid soluble polyethylene imine, poly 4-vinyl pyridine, poly 2-vinyl pyridine, poly Z-methyl S-vinyl pyridine, poly 2-vinyl quinoline, poly dimethylamino ethyl acrylate, poly dimethyl amino ethyl methacrylate, poly diethylamino ethyl acrylate, poly diethylamino ethyl methacrylate and poly vinylpyridine metho-p-toluene sulfonate. All of these materials may be classified as poly-cationic reagents having satisfacto hydrophilic properties.
  • Polymeric amines and polymeric quaternary ammonium compounds which have not been found useful in practicing the present invention, and which show either no activity or else enhance emulsion stability, are exemplified by the Hofmann degradation products of poly acrylamide, such as are described in U.S. Patent No. 2,729,560 to House et al., and by alkylated poly vinyl pyridines wherein the alkyl group contains more than about 2 carbon atoms.
  • poly 4-vinyl-N-n-butyl pyridonium bromide such as described by Fuoss and Strauss (Annals of the New York Academy of Sciences, 51, 836-851, May 1949) promotes the wetting of solids by the organic phaseto such an extent that all of the solids are transferred to the organic phase.
  • the N-but yl group is of suflicient hydrophobicity so that when exposed to the liquid-liquid environment, wetting by the organic phase is favored over wetting by the aqueous phase. This reversal of characteristics is believed tobe attributable to the fact that the substituent alkyl group is wholly nonpolar and large enough, when oriented toward the exterior liquid phases, to promote wetting by the organic phase.
  • poly vinyl pyridine may be quaternized with ethylene chlorohydrin and the resultant hydroxyethyl ammonium quaternary reacted with a molar equivalent of ethylene oxide to give a product of the structure:
  • D. enPom-m-om-onr-on The poly ethylene oxide quaternary function on the pyridine nitrogen now introduces suflicient hydrophilic character to the molecule to overbalance the hydrophobic properties of the introduced carbon atoms, and the resulting product is operative in practicing the present inslurry with a volume of hexane equal to about one-tenth the volume of the slurry to be tested, results in little or no transfer of solids to the hexane phase. If, on the other hand, solids are transferred in significant amounts to the hexane phase, then the tested product does not exhibit a proper degree of hydrophilic character and therefore is not operative in accordance with the process of the present invention.
  • polycationic materials or reagents described herein for the treatment of turbid leach liquors are referred to in the claims as being of hydrophilic character, it is understood that the polycationic material or reagent has a proper degree of hydrophilic character as determined by the above described test.
  • the Hofmann degradation products of poly acrylamide are apparently inoperative due to their carboxylic acid content which arises from inadvertent hydrolysis of the amide groups. As a result, these materials have very limited solubility in acid solutions, and in neutral solutions they react with the amine extractant to form insoluble poly soaps.
  • the efiiciency of the polymeric amines and polymeric quaternary ammonium compounds described herein varies from one species to another and is affected to some extent by such variables as the degree of polymerization (molecular weight), and efiective hydrophilic properties of the polymer.
  • the hydrophilic properties may also vary with molecular Weight, equivalent weight of the monomer unit, and other factors.
  • the dosage required per unit of Weight of solids suspended in the aqueous leach liquor will also vary depending upon the types of clays which are present in the slimes, since the ion exchange properties of the solids will vary from one clay to the next. It is, therefore, impractical to attempt to fix a. definite lower limitof dosage.
  • effective dosage in amine extraction systems generally involves application of about 0.1% by weight of polymer based on the total solids content of the aqueous leach liquor for the most active polymers, such as a high molecular Weight poly Z-methyl 5-vinyl pyridine; up to as high as 4-5% by weight of polymer based on total solids content of the aqueous leach liquor for some relatively inactive polymers, such as excessively high molecular weight poly ethylene imine samples which are of such a degree of polymerization that the polymer ,exhibits only very limited solubility in the presence of multivalent anions such as sulphate.
  • active polymers such as a high molecular Weight poly Z-methyl 5-vinyl pyridine
  • some relatively inactive polymers such as excessively high molecular weight poly ethylene imine samples which are of such a degree of polymerization that the polymer ,exhibits only very limited solubility in the presence of multivalent anions such as sulphate.
  • the upper limit of dosage is dictated by economies, since there appears to be no upper dosage limit in terms of efiiciency of emulsion inhibition. For example, a tenfold excess of the slime suppressing reagents described herein over the minimum required dosage which effects clean separation between the two liquid phases does not have any deleterious effect on emulsion inhibition.
  • a factor which does set an upper limit on dosage is that some of the polymeric amines or poly quaternary ammonium compounds, particularly those of higher molecular weight, when used in excess will react with and precipitate a variety of metals which may be present in solution as anions or anionic complexes.
  • such anions or anionic complexes may be exemplified by molybdate, vanadate and chromate.
  • the dosage be regulated to give I the desired phase separationwithout incurring loss of product through precipitation by the slime suppressing reagent.
  • An easily controlled variable which plays an important role in the above mentioned phenomenon of irreversible precipitation of anions and anionic complexesjby the polycationic material used as a slime suppressing lreagent is that of increasing the intrinsic hydrophilic character and thereby the water solubility of the polycationic mate rial, and of its anionic complexes, by introduction of water solubulizing groups along the polymer chain. This may be accomplished by either copolymerizing the cationic monomer with polar hydrophilic monomers or by introduction of such groups into the preformed homo polymer.
  • a monomeric polymerizable amine may be copolymerized with such polar vinyl monomers as vinyl acetate (with subsequent hydrolysis to vinyl alcohol) vinyl methyl ether, acrylamide, simple N-alkyl acrylamides, N-vinyl pyrrolidone, methyl acrylate or methyl vinyl ketone; or a preformed polymer may be alkylated or quaternized with ethylene oxide or ethylene chlorohydrin to introduce water solubilizing groups such as the hydroxy ethyl group, as hereinbefore described.
  • the resulting products may be classified as polycationic sub stances with improved hydrophilic and water solubility properties.
  • the minimum dosage is much less for identical turbid liquors to be contacted during the metal extraction step with tributyl phosphate in an organic solvent that when the organic selective solvent is a suitable amine.
  • a given polymer effective at a given dosage in an amine extraction system will, in general, be equally effective at as little as one-fifth of this dosage when tributyl phosphate is the selective solvent.
  • Example I A leach liquor obtained by acid leaching a typical molybdenum ore was treated and settled to provide araw desanded pulp containing 9.7% solids. A portion of this pulp was filtered to afford a clear liquor to which varying amounts of pulp were added in order to prepare turbid liquors varying in solid content.
  • Table I I contains tabulated data illustrating the dosage of slime treating agent and the separation behavior for the respective solvent systems.
  • aqueous solution is contacted during the solvent extraction step with a neutral to basic water immiscible organic solvent extractant for the metal values to thereby obtain a metal loaded extractant, the aqueous solution containing suspended slimes which detrimentally affect the extraction process
  • the improvement comprising treating the aqueous solution with effective quantities of a polycationic material of hydrophilic character having a molecular weight of at least,5,000 and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slirnes hydrophilic in nature and inhibit emulsion formation.
  • aqueous solution containing suspended slimm which detrimentally affect the extraction process
  • the improvement comprising treating the aqueous solution with effective quantities of a polymeric amine of hydrophilic character having a molecular weight of at least 5,000 and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slimes hydrophilic in nature and inhibit emulsion formation.
  • the improvement comprising treating the aqueous solution with effective quantities of poly 2-vinyl pyridine metho-p-toluene sulfonate of hydrophilic character having a molecular weight of at least 5,000 and less values from their aqueous solutions wherein the aqueous solution is contacted during the solvent extraction step with a neutral to basic Water immiscible organic solvent extractant for the metal values to thereby obtain a metal loaded extractant, the aqueous solution containing suspended slimes which detrimentally affect the extraction process, the improvement comprising treating the aqueous solution with etfective quantities of poly Z-methyl -vinyl pyridine of hydrophilic character having a molecular weight of at least 5,000 and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slimes hydrophilic in nature and inhibit emulsion formation.
  • the aqueous solution is contacted during the solvent extraction step with a neutral to basic organic water immiscible solvent extract-ant for the metal values to thereby obtain a metal loaded extractant, the aqueous solution containing suspended slimes which detrimentally affect the extraction process
  • the improvement comprising treating the aqueous solution with effective quantities of poly 2-vinyl quinoline of hydrophilic character having a molecular weight of at least 5,000 and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slimes hydrophylic in nature and inhibit emulsion formation.
  • the improvement comprising treating the aqueous solution with eifective quantities of poly dimethylamino ethylmethacrylate of hydrophilic character having a molecular weight of at least 5,000; and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slimes hydrophilic in nature and inhibit emulsion formation.
  • the improvement comprising treating the aqueous solution with eifective quantities of poly 4-vinyl pyridine of hydrophilic character having a molecular weight of at least 5,000 and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slimes hydrophilic in nature and inhibit emulsion formation.

Description

2,955,932 HYDROMETALLURGICAL PROCESS Mayer B. Goren, Denver, Colo assignor to Kerr-McGee Oil Indnstrles,'1ne., a corporation of Delaware No Drawing. Filed Apr. 22, 1957, Ser. No. 654,080 20 Claims. (Cl. 75-121) This invention relates to improvements in hydrometallurgical processes and more particularly to emulsion inhibition in hydrometallurgical solvent extraction processes wherein an aqueous solution containing metal values to be concentrated by solvent extraction also contains troublesome slimes.
Research efforts in hydrometallurgy have resulted in the development of an impressive variety of solvent extraction processes designed to extract metals selectively from leach liquors into a water immiscible organic selective solvent from which the metal may subsequently be recovered by various stripping agents. Other solvent extraction processes are designed to extract anion complexes with very high selectivity from their aqueous solutions for the purpose of securing very high grade 25 concentrates or products. The water immiscible organic selective solvents may be acidic in nature such as the monoordi-alkyl hydrogen phosphates, or neutral in nature, such as the tri-alkyl phosphates, or basic in nature, such as the more recently developed organic amine selective solvent extractants. The present invention is concerned only with those water immiscible organic selective solventswhich are either neutral or basic in nature and not with those which are acidic in nature. The organic selective solvents which are acidic in nature are not suitable for use in accordance with the present invention.
There are comparatively few waterinimiscible organic selective solvents which may be classified as neutral in nature, such as tri-butyl phosphate or other tri-alkyl phosphates, diethyl ether, hexane; and cetrain esters and ketones. However, a wide variety of amines have activity in organic solvent extraction processes and are well known to the art. In general, the more satisfactory amine selec- 45 tive solvents are relatively high molecular weight and primary, secondary or tertiary alkyl amines (mono, di or tri-alkyl amines) which are insoluble in dilute acidic solutions. The lower alkylated amines are, in general, soluble in dilute acid solutions and are not useful in solvent extraction processes, as is well understood in the art. Generally, as the size of the alkyl substituent increases, the corresponding amine salts become less and less soluble in water or dilute acid solutions and more soluble in organic solvents. Examples of suitable amines which have been found to be useful to various extents as organic selective solvent and which are very satisfactory in practicing the present invention are illustrated below in Table I. The amines illustrated therein are chosen at random and are intended as being only representative of a very large group of active amines.
Patented Oct. 11, 1960 The chemistry of amine extraction processes isthought to be largely similar to the chemistry of ion exchange absorption of metals from their aqueous solutions by anion exchange resins; i.e., the metal is most probably complexed by the liquid or solid amine as a simple or complex anion. In the more successful solvent extraction processes, the amine-anion complex is selectively soluble.
in the organic phase, the amine solvent normally being dissolved in a water immiscible inert organic solvent such as kerosene, naphtha, benzene, chloroform, etc. In practicing a conventional solvent extraction process, the solution of amine in organic solvent is intimately contacted with an aqueous leach liquor containing metal values to be concentrated, thereby forming the amine-metal anion complex. Successive contacts with fresh amine in organic solvent serves to transfer essentially the entire content of metal values to be concentrated from the aqueous leach liquor into the organic phase to thereby provide a metal loaded extraction solution. This extraction solution then may be stripped with any suitable stripping agent to provide a concentrate of the extracted metal values in the stripping solution and a regenerated amine in water immiscible inert organic solvent. The resulting strip solution is then further processed in accordance with prior art processes to produce a concentrate of the metal values or a metal containing product which, in turn, may be further processed to the desired metal. The regenerated amine in water immiscible inert organic solvent may then be recycled in the process.
One serious problem encountered in liquid-liquid extraction processes of the type above described is emulsion formation, which often gives rise to expensive losses of the selective organic solvent in instances where the organic phase, i.e., the solution of organic selective solvent in water immiscible inert organic solvent, is emulsified into the barren aqueous phase. Also, in instances where the aqueous phase, i.e., the leach liquor, is trapped in the organic phase, the impurities contained therein are removed with the organic phase and subsequently stripped therefrom during the stripping step. The resulting strip solution contains undesirable amounts of impurities which in turn are present in the metal concentrate or product finally prepared therefrom. 1
In general, the proper choice of organic selective solvent and the water immiscible inert organic solvent will minimize emulsion difficulties in solvent extraction operations dealing with wholly clarified sparkling liquors. For example, proper selection ofsubstituent alkyl groups on amine organic selective solvents will minimize the surface-active properties of the molecule so that emulsion formation is largely eliminated. However, when the aqueous leach liquors being treated are turbid, as frequently arises in hydrometallurgical practice, emulsion difiiculties become multiplied many times and particularly in the instance of the amine extractants.
Turbidity in slightly dirty leach liquors is rarely attributable to the so-called sand fraction of the pulp, and is generally due to fractions of the finer, clayey slime portion. The slime portion contains microscopic particles which resist settling in a thickener, or which may pass through a clarifying filter. Such particles are highly hydrated suspended clay fractions oflarge surface area and exhibit the usual ion exchange characteristics of clays. It is this property whichmost likely gives rise to the vicious emulsification tendencies of the above mentioned turbid liquors when contacted with the aminein-organic solvent and to lesser extent with other types of selective solvents. When such highly hydrated suspended clay fractions are contacted with an organic solution of an amine, the latter may be strongly absorbed on the surface of the clay particles, with the hydrocarbon chain of the molecule being oriented outward to thereby expose a hydrophobic surface. As a consequence, the clay-amine complex is wet by the organic layer and'is carried into the organic phase along with considerable amounts of aqueous phase which is trapped by the hydrated clay particles. The presence of such solids in the organic phase appears to promote the carrying of the rafiinate into' the organic phase and thus serves to stabilize theemulsion. In consequence, there is no clean break between the aqueous phase and the organic phase, and separation between the two phases is ditficult and loss of solvent to the aqueous phase occurs. In addition, the amine which is absorbed on the clay particles is lost.
It is an object of the present invention to suppress the deleterious effects of slimes in solvent extraction processes.
It is a further object of the present invention to provide a novel process for treating slimes contained in leach liquors whereby the tendency of the slimes to promote emulsification of the organic layer in a solvent extraction process is inhibited.
It is still a further object of the present invention to provide a process wherein emulsion formation stabilized by solidspresent in a turbid leach liquor is prevented.
It is still a further object of the present invention to provide a novel process to prevent adsorption of organic selective solvents on the ion exchange sites of suspended solid particles contained in a turbid leach liquor.
It is still a further object of the present. invention to provide a novel process for preventing the carrying of solids, together with occluded rafiinate, from a turbid leach liquor into the organic extract phase during a solvent extraction process.
It has been discovered that ifleach liquors suspended solids are treated with any one or a combination of a number. of organic reagents, i.e., poly cationic materials, preferably, prior to contacting with a suitable organic selective solvent in water immiscible inert organic solvent, adsorption of the selective solvent on the surface of the slime particles can be prevented. Thus, the solids or slimes are not carried into the organic layer and theformation of a solid-stabilized emulsion is prevented.
The reagents which have been found to be most etfective in practicing the present invention have the following general characteristics:
(1) The reagent must be strongly adsorbed by the solids or slimes in the leach liquor, largely saturating the ion exchange sites, and should not be desorbed and replaced by the selective solventduring the subsequent solventextraction step.
(2) The reagent must be hydrophilic in nature and, after adsorption on the surfaces of the solids or slimes, form a hydrophilic exterior surface oriented toward the liquid-liquid system, thereby repelling the organic phase and being strongly wet by the aqueous phase.
(3) If the reagent is used in'excess beyond the adsorptive capacity of the suspended solids or slimes, the reagent should not. possess sufiicient surface-active properties to promote emulsification.
(4) The reagent should be soluble in the presence of various anions and cations in the aqueous leach liquor, although certain reagents of somewhat limited solubility are effective due to the relatively small dosage required.
(5) The reagent should not react with the selective organic solvent. I
(6) Preferably, thereagent should be effective at low dosages and, from an economic standpoint, the reagent should be low in price.
'In accordance with the present invention, turbid leach liquors containing suspended solids or slimes 'are first treated with one or a combination of a variety of water or acid soluble poly cationic materials such as polymeric 4 molecular weight of at least about 5,000 and higher (e.g., to the degree of polymerization which afiords a product having characteristics bordering on insolubility in dilute acid solutions containing multivalcnt anions such as sulfate, and which will therefore vary for individual polymers) and then subsequently contacted with a suitable extractant for the metal to beconcentrated such as a solution of tri-butyl phosphate or a suitable amine in kerosene. The foregoing treatment will afford suspensions wherein little or no solids are occluded and emulsified into the organic layer and a clean separation between the two liquid phases may be readily achieved. Also, the solids do not tend to collect at the interface of the two phases, but instead are either uniformly dispersed and/or settle in the aqueous phase. As above stated, it is generally preferable to treat the turbid leach liquor prior to the extraction step for best results but this is not always necessary. For example, in some instances, satisfactory results may be obtained by treatment with the reagent during or following the extraction step.
Among the polymeric amines and polymeric quaternary ammonium compounds which have been found to be very efiective are water or acid soluble polyethylene imine, poly 4-vinyl pyridine, poly 2-vinyl pyridine, poly Z-methyl S-vinyl pyridine, poly 2-vinyl quinoline, poly dimethylamino ethyl acrylate, poly dimethyl amino ethyl methacrylate, poly diethylamino ethyl acrylate, poly diethylamino ethyl methacrylate and poly vinylpyridine metho-p-toluene sulfonate. All of these materials may be classified as poly-cationic reagents having satisfacto hydrophilic properties.
Polymeric amines and polymeric quaternary ammonium compounds which have not been found useful in practicing the present invention, and which show either no activity or else enhance emulsion stability, are exemplified by the Hofmann degradation products of poly acrylamide, such as are described in U.S. Patent No. 2,729,560 to House et al., and by alkylated poly vinyl pyridines wherein the alkyl group contains more than about 2 carbon atoms. Thus, poly 4-vinyl-N-n-butyl pyridonium bromide such as described by Fuoss and Strauss (Annals of the New York Academy of Sciences, 51, 836-851, May 1949) promotes the wetting of solids by the organic phaseto such an extent that all of the solids are transferred to the organic phase. In this instance, the N-but yl group is of suflicient hydrophobicity so that when exposed to the liquid-liquid environment, wetting by the organic phase is favored over wetting by the aqueous phase. This reversal of characteristics is believed tobe attributable to the fact that the substituent alkyl group is wholly nonpolar and large enough, when oriented toward the exterior liquid phases, to promote wetting by the organic phase. However, certain modifications allow incorporaamines and quaternary ammonium compounds having a tion without deleterious effects of substituents having an equal or greater number of carbon atoms, provided that polar hydrophilic functions are introduced at-the same time to counterbalance the hydrophobic influence of the hydrocarbon substituent.
Thus, poly vinyl pyridine may be quaternized with ethylene chlorohydrin and the resultant hydroxyethyl ammonium quaternary reacted with a molar equivalent of ethylene oxide to give a product of the structure:
D. enPom-m-om-onr-on The poly ethylene oxide quaternary function on the pyridine nitrogen now introduces suflicient hydrophilic character to the molecule to overbalance the hydrophobic properties of the introduced carbon atoms, and the resulting product is operative in practicing the present inslurry with a volume of hexane equal to about one-tenth the volume of the slurry to be tested, results in little or no transfer of solids to the hexane phase. If, on the other hand, solids are transferred in significant amounts to the hexane phase, then the tested product does not exhibit a proper degree of hydrophilic character and therefore is not operative in accordance with the process of the present invention. Where the polycationic materials or reagents described herein for the treatment of turbid leach liquors are referred to in the claims as being of hydrophilic character, it is understood that the polycationic material or reagent has a proper degree of hydrophilic character as determined by the above described test. The Hofmann degradation products of poly acrylamide are apparently inoperative due to their carboxylic acid content which arises from inadvertent hydrolysis of the amide groups. As a result, these materials have very limited solubility in acid solutions, and in neutral solutions they react with the amine extractant to form insoluble poly soaps.
The efiiciency of the polymeric amines and polymeric quaternary ammonium compounds described herein varies from one species to another and is affected to some extent by such variables as the degree of polymerization (molecular weight), and efiective hydrophilic properties of the polymer. The hydrophilic properties may also vary with molecular Weight, equivalent weight of the monomer unit, and other factors. The dosage required per unit of Weight of solids suspended in the aqueous leach liquor will also vary depending upon the types of clays which are present in the slimes, since the ion exchange properties of the solids will vary from one clay to the next. It is, therefore, impractical to attempt to fix a. definite lower limitof dosage. However, it may be stated that effective dosage in amine extraction systems generally involves application of about 0.1% by weight of polymer based on the total solids content of the aqueous leach liquor for the most active polymers, such as a high molecular Weight poly Z-methyl 5-vinyl pyridine; up to as high as 4-5% by weight of polymer based on total solids content of the aqueous leach liquor for some relatively inactive polymers, such as excessively high molecular weight poly ethylene imine samples which are of such a degree of polymerization that the polymer ,exhibits only very limited solubility in the presence of multivalent anions such as sulphate.
The upper limit of dosage is dictated by economies, since there appears to be no upper dosage limit in terms of efiiciency of emulsion inhibition. For example, a tenfold excess of the slime suppressing reagents described herein over the minimum required dosage which effects clean separation between the two liquid phases does not have any deleterious effect on emulsion inhibition. A factor which does set an upper limit on dosage is that some of the polymeric amines or poly quaternary ammonium compounds, particularly those of higher molecular weight, when used in excess will react with and precipitate a variety of metals which may be present in solution as anions or anionic complexes. In certain acid solutions, such anions or anionic complexes may be exemplified by molybdate, vanadate and chromate. In instances where such anions or anionic complexes are to be ex tracted, it is necessary that the dosage be regulated to give I the desired phase separationwithout incurring loss of product through precipitation by the slime suppressing reagent.
An easily controlled variable which plays an important role in the above mentioned phenomenon of irreversible precipitation of anions and anionic complexesjby the polycationic material used as a slime suppressing lreagent is that of increasing the intrinsic hydrophilic character and thereby the water solubility of the polycationic mate rial, and of its anionic complexes, by introduction of water solubulizing groups along the polymer chain. This may be accomplished by either copolymerizing the cationic monomer with polar hydrophilic monomers or by introduction of such groups into the preformed homo polymer. Thus, a monomeric polymerizable amine may be copolymerized with such polar vinyl monomers as vinyl acetate (with subsequent hydrolysis to vinyl alcohol) vinyl methyl ether, acrylamide, simple N-alkyl acrylamides, N-vinyl pyrrolidone, methyl acrylate or methyl vinyl ketone; or a preformed polymer may be alkylated or quaternized with ethylene oxide or ethylene chlorohydrin to introduce water solubilizing groups such as the hydroxy ethyl group, as hereinbefore described. The resulting products may be classified as polycationic sub stances with improved hydrophilic and water solubility properties.
The minimum dosage is much less for identical turbid liquors to be contacted during the metal extraction step with tributyl phosphate in an organic solvent that when the organic selective solvent is a suitable amine. Thus, a given polymer effective at a given dosage in an amine extraction system will, in general, be equally effective at as little as one-fifth of this dosage when tributyl phosphate is the selective solvent.
Although individual polymers or a combination of polymers described herein are effective on slime pulps containing as high as 10-15% solids in suspension, treatment is more economical when applied to what may be classed as turbid liquors containing less than 1% and preferably as little as 0.1% or less of suspended solids. Hazy thickener overflow liquors which can be very troublesome to treat by solvent extraction processes fall into this category and respond very well to economic treatment without the need of polishing filters, the efiiuent from which may still be hazy and contain suflicient suspended solids to be troublesome.
Inasmuch as the solvent extraction step generally infresh surfaces will not be exposed during the subsequent solvent extraction step due to the formation of fresh uni treated surfaces of slimes and emulsion formation and/or transfer of solids to the organic phase may be effectively 1 inhibited.
The foregoing detailed description and the following specific example are for the purposes of illustration only, and are not intended as limiting to the spirit or scope of the appended claims. v
Example I A leach liquor obtained by acid leaching a typical molybdenum ore was treated and settled to provide araw desanded pulp containing 9.7% solids. A portion of this pulp was filtered to afford a clear liquor to which varying amounts of pulp were added in order to prepare turbid liquors varying in solid content.
Aliquots of well-agitated samples were taken, treated with varying dosages of the slime treating agents and then intimatelyicontacted with 25% by volume of an extractant comprising kerosene and 10% of an active metal value extraction solvent such as tributyl phosphate or a suitable amine. The layers were vigorously agitated for live minutes and the separation behavior of the phases was observed.
Table I I contains tabulated data illustrating the dosage of slime treating agent and the separation behavior for the respective solvent systems.
For the sake of simplicity, the slime treating agents are identified in Table II by the following Roman numerals:
I. Poly-2-vinyl pyridine metho-p-toluene sulfonate II. Poly Z-methyl S-vinyl pyridine (low degree polyvmerization) III. Poly 2-methyl 5-vinyl pyridine (high degree polymerization) IV. Polyethylene imine, molecular weight about 50,000
V. Poly 2-vinyl quinoline VI. Poly 4-vinyl N-n-butylpyridonium bromide VII. Poly dimethylamino ethyl methacrylate VIII. Poly 4v1nyl pyridine TABLE II Behavior of Solvent System Test No. Reagent Dosage Amine 'l'rihutyl Phosphate Percent None mostsolidstoorganimmost solids to organic. 0. s3 emulsion; solids to trace emulsion.
organic. 1.25 clean separation. clean separation.
0.5 emulsion Do. 1 do Do. 1.7 clean separation Do. 0.07 emulsion; solids to borderline-sl1ght organic. emulsion. 0.10 ...do clean separation. 0. 16 d 0. 0.21 borderlineslight D emulsion. 0. 3.. clean separation D 0.63 d Do. 1. 25 Do. 1.25 borderline.
5 horderlineslight clean separation.
' emulsion. 0.32 emulsion Do, 0.9 clean Separation". D 0.5 all solids to organic lsi n 1.0 do Dc... 5 do Do. 0. 8 emulsion; solids to clean separation.
organic. 2. 5 clean separation Do. 0.32 emulsion; solids to Do.
organic. 0.63 clean separation Do. 1.25 do Do.
l Dosage: Percent by weight oi polymer used in the treatment based on total weight oi solids present.
What is claimed is:
1. In a process for the solvent extraction of metal values from their aqueous solutions wherein the aqueous solution is contacted during the solvent extraction step with a neutral to basic water immiscible organic solvent extractant for the metal values to thereby obtain a metal loaded extractant, the aqueous solution containing suspended slimes which detrimentally affect the extraction process, the improvement comprising treating the aqueous solution with effective quantities of a polycationic material of hydrophilic character having a molecular weight of at least,5,000 and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slirnes hydrophilic in nature and inhibit emulsion formation.
2. The process of claim 1 wherein the aqueous solution is treated with 0.l5% by weight of polycationic material based upon the total weight of solids present in 4. The process of claim 3 wherein the treated aqueous solution is agitated to thereby'reducethe size of the flocs produced therein. I l
5. The process of claim 4 wherein the-aqueous solution is treated with 0.14% by weight of polycationie material based upon the total weight of solids present in the aqueous solution. v
6. In a process for the solvent extraction oflmetal values from their aqueous solutions wherein the aqueous solution is contacted during the solvent extraction step with a neutral to basic organic water immiscible solvent extractant for the metal values to thereby obtain a metal loaded extractant, the aqueous solution containing suspended slimm which detrimentally affect the extraction process, the improvement comprising treating the aqueous solution with effective quantities of a polymeric amine of hydrophilic character having a molecular weight of at least 5,000 and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slimes hydrophilic in nature and inhibit emulsion formation.
7. The process of claim .6 wherein the aqueous solution is treated with 0.15% by weight of polymeric amine based upon the total weight of solids present in the aqueous solution.
8. The process of claim 6 wherein the aqueous solution is treated with the polymeric amine prior to, the extraction step. i
9. The process of claim 8 wherein the treated aqueous solution is agitated to thereby reduce the size of the flocs produced therein. 1
10. The process of claim 9 wherein the'aqueous solution is treated with (Ll-5% by weight of polymeric amine based upon the total weight of solids present in the aqueous solution.
11. In a process for the solvent extraction of metal values from their aqueous solutions wherein the aqueous solution is contacted duringthe solvent extraction step with a neutral to basic organic water immiscible solvent extractant for the metal values to thereby obtain a metal loaded extractant, the aqueous solution containingsuspended slimes which detrimentally afiect the extraction process, the improvement comprising treating the aqueous solution with eiiective quantities of a polymeric ammonium compound of hydrophilic character having a molecular weight of at least 5,000 and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slimes hydrophilic in nature and inhibit emulsion formation.
12. The process of claim 11 wherein the aqueous solution is treated with 0.l5% by weight of polymeric ammonium compound based upon the total weight of solids present in the aqueous solution.
' 13. The process of claim 11 wherein the aqueous solution is treated with the polymeric ammonium compound prior to the extraction step.
14. The process of claim 13 wherein the treated aqueous solution is agitated to thereby reduce the size of the fiocs produced therein.
15. The process of claim 14 wherein the aqueous solution is treated with 0.1-5% by weight of polymeric ammonium compound based upon the total weight of solids present in the aqueous solution.
16. In a process for the solvent extraction of metal values from their aqueous solutions wherein the aqueous solution is contacted during the solvent extraction step with a neutral to basic water immiscible organic solvent extractant for the metal values to thereby obtain a metal loaded extractant, the aqueous solutioncontaining suspended slimes which detrimentally affect the extraction process. the improvement comprising treating the aqueous solution with effective quantities of poly 2-vinyl pyridine metho-p-toluene sulfonate of hydrophilic character having a molecular weight of at least 5,000 and less values from their aqueous solutions wherein the aqueous solution is contacted during the solvent extraction step with a neutral to basic Water immiscible organic solvent extractant for the metal values to thereby obtain a metal loaded extractant, the aqueous solution containing suspended slimes which detrimentally affect the extraction process, the improvement comprising treating the aqueous solution with etfective quantities of poly Z-methyl -vinyl pyridine of hydrophilic character having a molecular weight of at least 5,000 and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slimes hydrophilic in nature and inhibit emulsion formation.
18. In a process for the solvent extraction of metal values from their aqueous solutions wherein the aqueous solution is contacted during the solvent extraction step with a neutral to basic organic water immiscible solvent extract-ant for the metal values to thereby obtain a metal loaded extractant, the aqueous solution containing suspended slimes which detrimentally affect the extraction process, the improvement comprising treating the aqueous solution with effective quantities of poly 2-vinyl quinoline of hydrophilic character having a molecular weight of at least 5,000 and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slimes hydrophylic in nature and inhibit emulsion formation.
19. In a process for the solvent extraction of metal values from their aqueous solutions wherein the aqueous solution is contacted during the solvent extraction step with a neutral to basic organic water immiscible solvent extractant for the metal values to thereby obtain a metal loaded extractant, the aqueous solution containing suspended slimes which detrimentally afiect'the extraction process, the improvement comprising treating the aqueous solution with eifective quantities of poly dimethylamino ethylmethacrylate of hydrophilic character having a molecular weight of at least 5,000; and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slimes hydrophilic in nature and inhibit emulsion formation.
20. In a process for the solvent extraction of metal values from their aqueous solutions wherein the aqueous solution is contacted during the solvent extraction step with a neutral to basic organic water immiscible solvent extractant for the metal values to thereby obtain a metal loaded extractant, the aqueous solution containing suspended slimes which detrimentally aifect the extraction process, the improvement comprising treating the aqueous solution with eifective quantities of poly 4-vinyl pyridine of hydrophilic character having a molecular weight of at least 5,000 and less than that molecular weight represented by incipient insolubility in a dilute acid containing multivalent anions to render the slimes hydrophilic in nature and inhibit emulsion formation.
References Cited in the file of this patent UNITED STATES PATENTS 2,634,280 Tribalat et al Apr. 7, 1953 2,732,350 Clarke Jan. 24, 1956 2,740,522 Aimone et al. Apr. 3, 1956 2,817,645 Weisguber Dec. 24, 1957 FOREIGN PATENTS 154,799 Australia Ian. 19, 1954

Claims (1)

1. IN A PROCESS FOR THE SOLVENT EXTRACTION OF METAL VALUES FROM THEIR AQUEOUS SOLUTIONS WHEREIN THE AQUEOUS SOLUTION IS CONTACTED DURING THE SOLVENT EXTRACTION SOLVENT WITH A NEUTRAL TO BASIC WATER IMMISCIBLE ORGANIC SOLVENT EXTRACTANT FOR THE METAL VALUES TO THEREBY OBTAIN A METAL LOADED EXTRACTANT, THE AQUEOUS SOLUTION CONTAINING SUSPENDED SLIMES WHICH DETRIMENTALLY EFFECT THE EXTRACTION PROCESS, THE IMPROVEMENT COMPRISING TREATING THE AQUEOUS SOLUTION WITH EFFECTIVE QUANTITIES OF A POLYCATIONIC MATERIAL OF HYDROPHILIC CHARACTER HAVING A MOLECULAR WEIGHT REPRESENTED LEAST 5,000 AND LESS THAN THAT MOLECULAR WEIGHT REPRESENTED BY INCIPIENT INSOLUBILITY IN A DILUTE ACID CONTAINING MULTIVALENT ANIONS TO RENDER THE SLIMES HYDROPHILIC IN NATURE AND INHIBIT EMULSION FORMATION.
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3007793A (en) * 1960-05-27 1961-11-07 Allis Chalmers Mfg Co Preparation of spectrographically nickel-free cobalt
US3052516A (en) * 1959-02-10 1962-09-04 Gen Mills Inc Process for recovering tungsten values from solution
US3056648A (en) * 1960-08-26 1962-10-02 Du Pont Process for extracting cyanides
US3146193A (en) * 1960-04-04 1964-08-25 Dow Chemical Co Aqueous suspension clarification method
US3257164A (en) * 1961-07-21 1966-06-21 Pennsalt Chemicals Corp Recovery of vanadium
US3367749A (en) * 1963-02-20 1968-02-06 Monsanto Co Purifying phosphoric acid using an amine extractant
US3414403A (en) * 1966-04-08 1968-12-03 Atomic Energy Commission Usa Silver separation from an acid solution
US3446720A (en) * 1965-01-27 1969-05-27 Us Interior Preparation of high-purity nickel and cobalt
US3472767A (en) * 1968-01-31 1969-10-14 Hercules Inc Waste treatment
US3473919A (en) * 1967-06-05 1969-10-21 Armour Ind Chem Co Process for separating iron from aluminum
US3495934A (en) * 1967-02-07 1970-02-17 Forsch Inst Fuer Ne Metalle Method for extracting rhenium from aqueous solutions
US3572504A (en) * 1966-05-11 1971-03-30 Auby Prod Chim Method for the flotation of oxidic ores with calcareous and dolomitic gangue
US3607236A (en) * 1969-09-22 1971-09-21 Parkman T Brooks Reclaiming of superalloy scrap
US3856917A (en) * 1972-04-14 1974-12-24 Ugine Kuhlmann Process for treating residual solutions containing hexavalent chromium compounds

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2634280A (en) * 1948-03-06 1953-04-07 S I F E M Process for the extraction of rhenium and analogous elements
US2732350A (en) * 1956-01-24 Polyelectrolytes comprising copoly-
US2740522A (en) * 1953-04-07 1956-04-03 American Cyanamid Co Flotation of ores using addition polymers as depressants
US2817645A (en) * 1954-06-30 1957-12-24 Hercules Powder Co Ltd Reaction of polyvinylphthalimides and alkylene polyamines and products thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2732350A (en) * 1956-01-24 Polyelectrolytes comprising copoly-
US2634280A (en) * 1948-03-06 1953-04-07 S I F E M Process for the extraction of rhenium and analogous elements
US2740522A (en) * 1953-04-07 1956-04-03 American Cyanamid Co Flotation of ores using addition polymers as depressants
US2817645A (en) * 1954-06-30 1957-12-24 Hercules Powder Co Ltd Reaction of polyvinylphthalimides and alkylene polyamines and products thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3052516A (en) * 1959-02-10 1962-09-04 Gen Mills Inc Process for recovering tungsten values from solution
US3146193A (en) * 1960-04-04 1964-08-25 Dow Chemical Co Aqueous suspension clarification method
US3007793A (en) * 1960-05-27 1961-11-07 Allis Chalmers Mfg Co Preparation of spectrographically nickel-free cobalt
US3056648A (en) * 1960-08-26 1962-10-02 Du Pont Process for extracting cyanides
US3257164A (en) * 1961-07-21 1966-06-21 Pennsalt Chemicals Corp Recovery of vanadium
US3367749A (en) * 1963-02-20 1968-02-06 Monsanto Co Purifying phosphoric acid using an amine extractant
US3446720A (en) * 1965-01-27 1969-05-27 Us Interior Preparation of high-purity nickel and cobalt
US3414403A (en) * 1966-04-08 1968-12-03 Atomic Energy Commission Usa Silver separation from an acid solution
US3572504A (en) * 1966-05-11 1971-03-30 Auby Prod Chim Method for the flotation of oxidic ores with calcareous and dolomitic gangue
US3495934A (en) * 1967-02-07 1970-02-17 Forsch Inst Fuer Ne Metalle Method for extracting rhenium from aqueous solutions
US3473919A (en) * 1967-06-05 1969-10-21 Armour Ind Chem Co Process for separating iron from aluminum
US3472767A (en) * 1968-01-31 1969-10-14 Hercules Inc Waste treatment
US3607236A (en) * 1969-09-22 1971-09-21 Parkman T Brooks Reclaiming of superalloy scrap
US3856917A (en) * 1972-04-14 1974-12-24 Ugine Kuhlmann Process for treating residual solutions containing hexavalent chromium compounds

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